Synthetic lubricants



Patented Mar. 14, 1950 SYNTHETIC LUBRICANTS William E. Garwood,Haddonfield, John W. Brooks, Wenonah, and Alexander N. Sachanen,Woodbury, N. J assignors to- Socony-Vacuum Oil Company, Incorporated, acorporation of New York No Drawing. Application June 8, 1949, Serial No.97,921

This invention has to do with the condensation 01 normal, alphamono-olefins, conjugated olefinic compounds and mercaptans or thiols.

A s is well known to those familiar with the art, oleiins havepreviously been polymerized; so also have vinyl aromatic hydrocarbons.Olefins and vinyl aromatic hydrocarbons have also been reacted together.copolymerization isgenerally incomplete. For example, when decene-l andstyrene are copolymerized at 600 R. an oil containing a polystyrenecloud at room temperature (20-25 C.) is formed. The oil thus obtainedpossesses approximately the same oxidation stability as uninhibitedPennsylvania SAE W mineral oils. Vinyl aromatic hydrocarbons, such asstyrene, when reacted with mercaptans form products characterized byvery low viscosity indices. In effect, then, when any two of theforegoing reactants-olefins, vinyl aromatic hydrocarbons, andmercaptans-are reacted together, the yield 19 Claims. (Cl. 252-482) Inthe latter instance, however,

of viscousoil is either insufiicien't or the viscous oil suffers fromone or more shortcomings, such as cloud formation, relatively lowoxidation stability or low viscosity index (V. 1.).

It has now been discovered thatcertain normal, alpha mono-olefinscondense with conjugated olefinic hydrocarbons and thiols, underconditions hereinafter" defined, with the formation of highly desirableviscous oils. These oils have molecular weights less than about 1000,generallywithin the range of 400 to 600. The oils so formed are freefrom the shortcomings of olefin-vinyl aromatic hydrocarbon copolymers,as illustrated by the l-decene-sty'rene copolymer referred to above.Further, the viscous oils of this invention are unusually stable.Catalytic oxidation stability tests demonstrate them to be superior tocondensation products of decene-l alone, to condensation products ofdecene-l and styrene, and to uninhibited Pennsylvania type mineral oils.The characteristics of the new oils are such as to make them outstandingsynthetic lubricants, for use alone or blended with other lubricants.

Reactonts The mono-olefin reactants of this invention are normal orstraight-chain alpha compounds, and contain from five to eighteen carbonatoms per molecule. liquid at temperatures oi! the order of 2025 C.Illustrative of such mono-oleflns are the followingz pentene-l,octene-l, decene-l, dodecene-l, octadecene-l and the like. Preferred ofsuch ole fins, however, are those having from eight to twelve carbonatoms per molecule, with decene-l representing a particularly desirableolefin It will be clear from the foregoing examples that an alpha olefinmay also be referred to as a l-oleiin.

Not only may the mono-olefins of the aforesaid character be usedindividually in this invention, but they may also be used in admixturewith each other. In addition, olefin mixtures containing a substantialproportion of such mono-olefins may be used. Preferred. of such mixturesare those containing a major proportion of a l-olefin or of l-olefins.Representative of such mixtures are those obtained by the cracking ofparaflin waxes and other paraflin products; those obtained from theFischer-Tropsch and related processes.

These hydrocarbon mixtures may contain, in addition to the l-olefin orl-olefins, such materials as: other olefins, paraffins, naphthenes andaromatics. I

Olefinic' compounds contemplated herein for condensation with normal,alpha mono-olefins and thiols are of conjugated character and includealiphatic compounds and alkenyl-substituted aromatic compounds. arecharacterized by the grouping I I I l and conjugated alkenyl-substitutedaromatic compounds are characterized by wherein A is an aromaticnucleus, an unsaturated Such mono-olefins are normally Conjugatedolefins group of which is in conjugated relationship with the alkenylgroup.

The coniugated paramnic hydrocarbons and derivatives thereof arerepresented by: butadiene, isoprene (Z-methyl butadiene)cyclopentadiene,

methyl isoprene; halogen-substituted materials benzene is {a typical andpreferred example.

Vinyl-diphenyl is another illustrative mononuclear compound.Representative ankenyl-- substituted poly-nuclear hydrocarbons are vinylnaphthalene, vinyl anthracene, etc. Derivatives j of such hydrocarbonsare also contemplated herein and include halogen-substituted materialssuch as p-chlorostyrene, alkoxy-su'bstituted 1 materials such asp-methoxy styrene, and the like. i

As will be noted from the character of the fore- 1 going typicalsubstituted, conjugated oleflnic hydrocarbons, substituent groups whichmaybe present are those which do not interfere with the condensation ofthe conjugated oleflnic compound with the aforesaid alpha mono-olefinand thiol. In other words, a substituent group which i may be present inthe conjugated oleflnic hydrocarbon is one which is substantially inertor un- 1 reactive in the condensation. The substituent group, however,generally modifies the character of the oil product, yet in all cases,the products are characterized by unusual stability and are useful aslubricants. By way of illustration. when p-chloro-styrene is used, thesynthetic lubricant formed possesses extreme pressure properties.Similarly, a fluoro-substituted styrene imparts additional stability tothe synthetic lubricant product as well as extreme pressure properties.

It will be understood, of course, that mixtures .of the aforesaidconjugated oleflnic hydrocar- 1 bons, and their aforesaid derivatives,may be used in place of the individual reactant. Similarly, mixturescontaining substantially, preferably major, proportions of one or moreof said con- .Iugated oleflnic compounds may be used. An example of sucha mixture is a crude styrene containing ethylbenzene.

Preferred of the alkenyl-substituted aromatic As indicated above,mercaptans or thiols are condensed herein with the aforesaid normal, al-

pha mono-oleilns and conjugated oleiinic compounds, and such compoundsmay be represented :by the general formula RSH, wherein R may behydrogen; a hydrocarbon group such as alkyl,

alkaryl, aryl, or aralkyl; or a heterocyclic grou such as thienyl (forexample) t-butyl thiophenol, t-butyl thionaphthol; arylthiols-thiophenol, e-thionaphthol, p-thlonaphcompounds, in view of theoutstanding character v of the products obtained therewith is styrene.

thol; aralbl thiols-bensyl thiol, phenyl 'ethyithiol; heterocyclicthiols-thiophenethiol, fur-anthiol. Thiophenethiol is described,together with methods for its preparation, in copending applicationSerial No. 721,454, filed January 10, 1947. Polythiols are alsocontemplated herein; however, such materials are generally used insmaller quantities than the monothiols.

Of the thiols represented by the general formula, those containing ahydrocarbon or heterocyclic group are preferred. Of the lattercompounds, n-butyl mercaptan, thiophenol and thiophenethiol' areparticularly preferred inasmuch as synthetic lubricants obtainedtherewith are of outstanding character.

Reaction conditions Condensation of the aforesaid reactants is affectedat elevated temperatures. It appears that temperatures as low as 400 F.and as high as 900 1". can be used in some instances, however,temperatures of the order of about 500 F. to about 800 F. are mostsatisfactory. The preferred temperature range. as shown'hereinbelow, isfrom about 600 F. to about 750 F.

Condensation is generally complete in from one to twenty hours,preferably from three to ten hours, with the higher reactiontemperatures being used for the shorter reaction periods and with thelower reaction temperatures being used for the longer reaction periods.a

Pressures ranging from atmospheric to 4000 lbs. per square inch may beused. In general, it is desirable to use suflicient pressure to maintainthe reactants in liquid state.

Proportion of reactants can be varied considerably to form productssuitable for different uses. With one molar proportion of normal, alphamono-oleilns as the basis, from about 0.01- to about one molarproportion of coniugated oleflnic compound, such as a vinyl aromaticcompound, and from about 0.001 to about one molar proportion of thiol,provide satisfactory products. Preferred proportions for formingoutstanding synthetic lubricants, however, are from about 0.05 to about0.5 molar proportion of conjugated oleflnic compound and from about 0.01to about 0.5 molar proportion of thiol, with one molar proportion ofnormal, alpha mono-olefin. By proper proportioning of reactants,synthetic lubricants may be obtained, or blending stocks for use withmineraloils to improve the latter in regard to oxidation stability,viscosity index, and/or pour point properties, may be obtained.Condensation products which are useful as lubricating oil additives oradjuvants in concentrations as low as two per cent in mineral oil toeflectively stabilize the latter against oxidation, are formed when arelatively large amount of thiol and conjugated oleilnic compounds areused. Products of the latter type however, are characterized by lowviscosity indices. As demonstrated hereinbelow in the illustrativeexamples, optimum conditions for forming the synthetic lubricants may beused, and the resulting synthetic lubricant may be reacted with anadditional quantity of a thiol with the same or diil'erent thiol to forma product of higher sulfur content and of increased oxidation stability.

It will be understood, of course, that the condensation is aided byproviding mixing of the reactants. This may be provided by using variousagitating means which are well known in the art. At the reactionconditions, the reactants are readily soluble and homogeneity is easilyobtained.

Examples In order to illustrate the prlnciples of this invention, theresults of a series of typical, and non-limiting, condensations are setforth in tabu- 6 be noted that the designation "N. N." refers to theneutralization number, which is a measure of the acidity of the oil. I

Styrene used in these condensations contained a a fraction of one percent of p-tertiary-butyl z'g g g grfi f g ggz g zgg iggz fi catechol,the latter acting as a stabilizer or polyican Instrument (10.). Thereactants were figi gm ggg ggh fi ama g charged to the bomb, which wasthen heated to v the desired temperature for the desired length of Byway of illustration the procedure unwed time Thereafter was cooled. andin run 1 Of Table I below, provided in detaiL A charged. The contents ofthe bomb were vacuum mixture of 336 parts by weight (3 molar prom!"distilled to remove unreacted materials. It should mus) mime 39 mm byweight benoted that the reaction times, recited as "Time, paportlmi) ofg 8 8 by s:

' Hours" in Table I, represent the time intervals 67 3 e g 13:

during which the bomb was maintained at the 15 was f i 1 a s a m g' {3desired temperature, and do not include the time er can Inst! r 9intervals necessary to heat the bomb and its conbomb head was secureapproximately 1500 tents to the desired temperature, and do not inpersquare inch of nltmgen was Pressured mm clude the time intervals.necessary to cool the the bomb to (meek for The pressure bomb after heatwthe bomb has been discom then released. the system was again closed andtil-lued. The condensation products discharged I the bomb was heated inthe 01 from the bomb, or other reaction vessel, were dis- 1V2 hours andheld at that temperature for ten tilled and filtered, as in the runsshown in Table' hours- During the Teactmn 1 To the condensation productsfrom lbs. per Square inch developed. cooling the the distillatefractions thereof, the refined oils bomb to room p ature, (70 F.),during a are identified as residual oils. The latter term Per 10d offibmlt three hours, the reaction Pmduct identifies the oils from whichuhreaeted matewas discharged into a la and pped under rials and productsof intermediate boiling range reduced p s r Hz) to a liqui temperhavebeen separated. ature of 420 F. and a vapor temperature of 345 F. All ofthe tests and analyses to which the re- A quantity, 118 parts by weight,of residual oil sidual oils in Table I were subjected are well wasobtained and was filtered through a thin coat known standard tests. Inthis connection, it will of a diatomaceous earth filter aid (SuperFlltrol) Table 1 Reaction Conditions Olefin Styrene Mercaptan ReierenceTemp. Time Max. Press. P P i i Name Moles l3? Moles Name 3? Moles F P I6' Weight Weight weight CONDENSATION or OLEFINS WITH STYRENE AND ALKYLMEROAP'IANS I Run:

1. Octane-l 336 s 39 0. 315 0 0. 001 601 10 200 Octane-2 330 a s9 0. 3150 0.067 002 10 150 Z-Ethylhexene-l. 3 30 0.315 0 0.067 002 10 200 3 as0.315 0 0.001 504 10% 100 s 30 0. 315 e 0. 001 59s 10 a00 s 39 0.515 00.001 s 10 a 39 0.315 a -0.001 100 3 800 3 39 0. 315 0 0. 067 150 a 1503 10 0.090 t 0. 001 053 10 200 s 39 0.315 0 0.051 052 10% 000 OLEFINSWITH STYRENE AND AROMATIC MEBCAPTANB 0 0. 054 001 1034 l00 0 0. 054 041lo 600 do o 0.054 054 9% 150 14 Product of Run l3 30 0. 273 605 5% (100CONDENSATION or OLEFINS WITH STYRENE AND HETEROCYCLIO MERCAPTANS Run:

15 Decene-l 420 s 30 0.003 601 10% also 16 Product 0! Run 15-- 220 0.011600 5 150 420 3 30 0.112 509 10 300 420 a as 0.011 04s 10 450 l 104 ls05 10 200 840 6.0 12 600 10% 400 CONDENSATION or OLEFIN WITH BUTADIENEAND ALKYL MERCAPTAN Run 21 Decene-l 420 a 21 0.5 N-butyl o 0.061 050 m4620' See footnotes at end of table.

Table I-Continued Residual Oil Reference Weight 01000 K. v. a x. v. r001Parts by rel-00110 Poin 100 210 F. v I. Point N. N. wei Yield r 00 c0 F.

CONDENSATION or 01.001100 WITH S'IYBENE AND ALKYL MERCAPTANS 110 01 2202 4. 00.0 -00 o. 2 0. 0120 0 00 40 11.0 00.24 4.00 42 -00 o. 1 0.01520.01 5.2 05. 01 4.00 0 50 124 04.45 5.20 000 -00 0.2 0.0111 0.04 112 24.1 11. 11 0. 10 110. 4 -00 0. 1 0. 0500 0. 01 150 00.0 21.11 4.20 120.4-00 02 0.0550 0.10 114 01.4 1000 0.00 125.1 -20 0.2 00545 0.20 v 121 20-2410 4.01 114.5 -5 0.2 0.0044 010 101 00 2400 4.10 120.0 -00 0.2 0. 04000.20 11 10 0 22 4.50 100 4 -00 0. 2 0. 0102 1.01

CONDENSATION or OLEFINS wrrn BTYRENE AND'ABOMATIO MERCAPTANS 15. 00 0.55 111. 0 -00 0. 1 o. 0001 0.10 22.01 4.00 110. 1 -0o 0. 1 0. 0020 0. 2020. 10 440 120.1 -0o 0.1 0.0501 0.10 2012 5.00 111.5 -5 0.0 0.0000 0.12

OLEFINS WITH STYRENE AND rm'rnaocyomo MEROAPTANS CONDENSATION or OLEFINwrrn BUTADIENE AND ALKYL MERCAPTAN Run 21 151 00.4 25. 14 5. 04 141 -00Nil 0. 0400 0. 12

1 From 390 g. of reaction product. Remainder used in run 14. From 228 g.of reaction product. Remainder used in rim 15. I Weight of totalreaction product from the indicated run.

olefin, oc'tene-l, reacts to form a substantially greater yield of asuperior oil than does either the corresponding 2-olefin and thecorresponding branched-chain ,octene. The oil product obtained byoctene-l has a. significantly higher V. I. than to three hours, are mostsatisfactory in that oil products of high viscosity index and low pourpoint are formed in relatively high yield. These salient features arerevealed in the following tabulation.

the oil products'jrom octene-2 and z-ethylhex- 1100051011001 Residual onene-l. This is summarized in the following tabufilm! lation: Run No. Yim K v e Pour 229" f g Weight 210 F? v 1 Point, Percent 00.

Residual 011 4 504 10% 12.4 5.20 00.0 00 02 0 02-: 20 mm OM11 r1010, K.v. 100 0 0114 0100 12511 -20 Weight 210 1 v. 1. 150 0 20.0 4.01 114.5 -5Percent 00.

1 Octene-l 01.0 4.10 00.0 2..- Octane-2 11.0 4.00 42 0 Z-ethylhexene-l6.2 4.39 0 A comparison of runs 6 and 9 indicates that as the proportionof styrene is increased the yield of residual oil increases withoutmaterially detract- Buns 4-8 show the influence of reaction temperatureand time upon the condensation of decene-Lstyrene and n-butyl mercaptan.Temperatm es of about GOO-750 F. with times of ten ing from thecharacter of the oil product. This feature is shown in the followingtabulation wherein a. blank run is shown for the condensation ofdecene-l and n-butyl mercaptan in the absence of styrene; in the blankrun, the proportions of mono-olefin and mercaptan are the same as inruns 6 and 9.

captan structure with the properties of the oil products. The straightchain structure of n-butyl mercaptan, in contrast to the branched-chainstructure of tertiary-butylmercaptan, appears to have a salutary eflectupon the yield and V. I. In addition, the oil product obtained from then-butyi compound has a lower sulfur content. These features are revealedin the following tabulation: 4

Residual oll Mercap' Run No m1 Yield, K.y.@ s w 1 M 3 1 210 F., v.1. g i

o n-ButyL 33.6 4.29 120.4 0.18 t-ButyL. 16.0 4.68 100.4 1.01

Oil products obtained with aromatic mercaptans are shown in runs 11-14.It will be noted that run 14 involves reaction of additional thiophenolwith the reaction product of run 13. Additional sulfur is introducedwithout affecting the characteristic properties of the oil.

A heterooyclic mercaptan, thiophenethiol, is shown in runs 15-19. Afurther illustration of reacting the olefin, vinyl aromatic andmercaptan under optimum conditions to obtain a residual oilor highyield, high viscosity and high viscosity index, and thereafterincreasing the sulfur content with the additional mercaptan, is shown byruns 15 and 16. This procedure is preferred when producing oil blendingstocks of relatively high sulfur content, where viscosity index and pourpoint of the oils blended therewith are improved by virtue of the highviscosity index and low pour point of the synthetic blending stocks.Runs 15, 17 and 19. illustrate the direct of the quantity of thiol usedin the condensation. When the molar proportion of thiol is increasedsuch that the olefin:styrene:thlol ratio is 1 1:1, the viscosity indexof the oil product falls on considerably, specific gravity increases andthe sulfur content is increased greatly. The oil product of run 19,finds utility as a lubricant in operations wherein high viscosity indexis not required and also finds utility as an oil addition agent forlubricating oils.

Run 20 is shown herein to demonstrate the difference between an oilproduct obtained by condensation of a l-olefln and a vinyl aromaticcompound in the absence of a thiol, and an oil product obtained with athiol. An effective comparison is provided by runs 5. 11, 15 and 20. Itwill be clear that the oil obtained in run 20, in which no thiol wasused, has excellent viscosity index and rate of 10 liters per hour. Thetest tube is heated 10 pour point properties, but has an undesirablyhigh cloud point, 60' F. In contrast, the oils of runs 5, 11 and 15 havelow cloud points. Emphasizing this relationship, the salient features ofthese runs are tabulated below:

Mercaptan Run Deoene-i, Styrene, ig No 1 e M Cloud ropn. ropn. 0 er NamePropn. Pt., "F.

20 6 0. 75 None- +00 5 3 0. 375 n-Butyl.. 0. 007 20 11 3 0.375 Thlohenol... 0. 054 -28 15 3 0. 375 3-tlhli oplleno- 0.008 34 Residual Oil pone 0 Run Molar Yield, K. v. s,

Propn Wei ht 210 F V. I Wei ht Per ent Cs. 1 Per eat 20 0-1 63.6 4.80131.3 1s 0. 00s as 4.11 130. 1 o. 25 17 0.112 14.0 4.08 104.1 6.38 19 l.0 30 0. 59 30. s 19. 9-1

It will be seen that the advantages obtained by the use of thiols are atthe expense of yield, but it must be kept in mind that the oil obtainedwithout a thiol is characterized by a poly-styrene cloud and is notusable as such.

Run 21 illustrates an excellent synthetic oil obtained with butadiene asthe polyolefinic reactant.

That the residual oils of this invention have excellent stability isshown by results of a catalytic oxidation test, the results being shownbelow in Table II. This oxidation test reveals the stability of oilstoward catalytic oxidation.

The test oil, 25 00s., is placed in a 200 x' 25 mms. test tube with 15.6square inches of sand-blasted iron wire; 0.78 square inches of polishedcopper wire, 0.87 square inch of polished aluminum wire, and 0.167square inch of polished lead plate. Dry air is passed through the sampleof oil at a.

at 260 F. for 40 hours in an aluminum block bath. The results reportedat the end of the test are: neutralization number (N. N.) percentviscosity increase at 210 F. sludge and lacquer; lead weight loss (inmilligrams); and appearance of copper. The oil is compared with areference oil of similar viscosity and is rated on the basis ofviscosity increase, N. N. increase, sludge and lead weight loss. Amaximum of 3 demerits is assigned to each factor rated. The sum of thedemerits for an oil is called the stability number and ranges from'l to12. The reference mineral oils, solvent-refined Pennsylvania oils, hav astability number of 6 to 7.

Table II.-Oa:idation stability of oils 6 Cent Slnd Pb Lo Stabilit on N.N. 210 F Visooslt Copper Coil Y cl more: Tube Mg. Number 10W MineralBase Stock L... 16 12.91 125 N11 236 6 or 7 un20 as 0.44 90.2 Nil DullCoupon--. ma 0 PRODUCTS FROM CONDENSATION OF OLEFINS WITH STYRENE ANDALKYL MERCAPTANB Run 6 .8 3.2 Run 10 .0 7.4

Nil.

NIL.-."

PRODUCTS FROM CON DENSATION OF OLEFIN S WITH STYRENE AND AROMATICMERCAPTANB PRODUCTS FROM CONDENBATION (1;

Nll 251.3 5 N11 Brown Shim... 243.2 7 Nil 159 2 OLEFINS WITH STYRENE ANDHETEROCYGLIC EROAPTANS Run 15 5.0 4. 97 20.9 NI] Brown Staln. 242.6 3Run 16.--- 0.8 4. 62 4.6 Ni. DarkBrown.- 36. 6 0 Run 17 1.1 4.36 6.8 NBlack Stain. 36.3 0 Run 18 10.8 7.07 53.6 N Brown Stain 245.8 6 Run 1927 in 10W Base Stock 1.8 6.27 10.1 N l Brassy 18.8 0 Run 19.6 o In 10WBase Stock 15.0 10.08 71.1 N d 199.1 4

PRODUCT FROM OONDENSATION OF DECENE-l WITH BUTADIENE AND N-BUTYLMERCAP'IAN Run 21 12. 5 11. 86 134 Nil.

1 Average values.

The results presented in Table 11 above, reveal that a solvent-refinedPennsylvania mineral oil, SAE 10W mineral oil base stock, which isconsidered in the art as a relatively stable mineral oil, has astability number of 6-7 in the test described above. Similarly, theresidual oil of run 20, obtained by condensation of decene-l andstyrene, without a thiol, has a stability number of 6; this istheresidual oil having a cloud point of +60 F. In contrast, the residualoils of runs 6 and 10, obtained by condensation of decene-l withstyrene, and with n-butyl mercaptan and t-butyl mercaptan, respectively,are substantially more stable for they have stability ratings of zero. 1Residual oils of runs 12 and 13, obtained with thiophenol were lessstable than those obtained with the butyl mercaptans, but were as stableas the mineral oil base stock. Stability numbers for with morethiophenethiol was resorted to, an improvement in stability was realized(zero as compared with 3). This is shown by the oils of runs 15 and 16.In run 17 a larger amount of thiophenethiol was used in the initialreaction than was used in run 15, and a stability number of zerocharacterized the product. In run 19,

still more thiophenethiol was used. The mineral oil base stock waseffectively stabilized when 2% of the residual oil of run 19 wasincorporated therein; however, 0.5 per cent of this residual oil wasinsuflicient for this purpose. It will be recognized, therefore, that inall instances the new synthetic oils are equal to or better than an SAE10W Pennsylvania motor oil in every respect.

As will be evident from the data presented above in Tables I and II, thecondensation products of this invention are highly desirable lubricantsper se. They are also of considerable value as blending agents for otherlubricating oils. In view of the inherent stability of the syntheticoils, they impart stability to the oils with which they are blended. Soalso, they impart desirable viscosity index (V. I.) and pour pointcharacteristics to the oils in combination therewith, for, as indicatedabove, they have advantageous viscosity index and pour point properties.In short, the synthetic oils find utility in upgrading other lubricants.Typical oils with which the synthetic oils may be blended are mineraloils such as are normally used in internal combustion andturbineengines. When so blended, the synthetic oils may comprise themajor proportion of the final blended oil, or may even comprise a minorproportion thereof. For example, although used only in the amounts ofthe order of 1-10 per cent, the synthetic oils improve the stability ofmineral oils, such as SAE 10 and 20 Pennsylvania type oils.

One or more of the individual properties of the synthetic lubricants ofthis invention may be further improved by incorporating therewith asmall, but effective amount, of an addition agent such as anantioxidant,a detergent, an extreme pressure agent, a foam suppressor, a viscosityindex (V. I.) improver, etc. Antioxidants are wellknown in the art, andare generally characterized by phosphorus, sulfur, nitrogen, etc.content; representative of such materials is an oil-soluble,phosphorusand sulfur-containing reaction product of pinen and phosphoruspentasulflde. Typical detergents which may be so used are metal salts ofalkyl-substituted aromatic sulfonic or carboxylic acids, as illustratedby diwax benzene barium sulfonate and barium phenate, barium salt of awax-substituted phenol carboxylic acid. Extreme pressure agents are wellknown; illustrating such materials are numerous chlorine and/or sulfurcontaining compositions, one such material being a chlornaphthaxanthate. Silicones, such as dimethyl silicone, may be used toillustrate foam suppressing comabout 0.001 to about one molar proportionof a thiol.

positions. Viscosity index improving agents which may be used aretypified by polypropylenes, polyisobutylenes, polyacrylate esters, andthe like.

contemplated also as within the scope of this invention is a method oflubricating relatively moving surfaces by maintaining therebetween afilm consisting of any of the aforesaid oils.

It is to be understood that the foregoing de-. scription andrepresentative examples are nonlimiting and serve to illustrate theinvention, which is to be broadly construed in the light of the languageof the appended claims.

We claim:

1. The method of preparation of a viscous oil, which comprises:condensing, at a temperature between about 500 F. and about 800 F. for aperiod of time sufficient to etlect condensation,

one molar proportion of a normal, alpha monoolefin having from five toeighteen carbon atoms per molecule, from about 0.01 to about one molarproportion of a conjugated olefinic hydrocarbon and from about 0.001 toabout one molar proportion of a thiol.

2. The method of claim 1 wherein the temperature is between about 600 F.and about 750 F.

3. The method of claim 1 wherein the monoolefin has from eight to twelvecarbon atoms per molecule.

4. The method of claim 1 wherein the conjugated olefinic hydrocarbon isan alkenyl-substituted aromatic hydrocarbon.

5. The method of claim 1 wherein the conjugated olefinic hydrocarbon isa vinyl-substituted aromatic hydrocarbon.

6. The method of claim 1 wherein the thiol is an alkyl thiol.

7. The method of claim 1 wherein the thiol is an aryl thiol. 1

8. The method of claim 1 wherein the thiol is a heterocyclic thiol.

9. A new composition of matter comprising, a sulfur-containingcondensation product obtained by: condensing, at a temperature betweenabout 500 F. and about 800 F. for a period of time sufficient to effectcondensation,v one molar proportion of a normal, alpha mono-olefinhaving from five to eighteen carbon atoms per molecule,

from about 0.01 to about one molar proportion of a conjugated olefinichydrocarbon and from 10. The composition of claim 9 wherein thetemperature is between about 600 F. and about 11. The composition ofclaim 9 wherein the mono-olefin has from eight to twelve carbon atomsper molecule.

12. The composition of claim 9 wherein the conjugated olefinichydrocarbon is an alkenylsubstituted aromatic hydrocarbon.

13. The composition of claim 9 wherein the conjugated olefinichydrocarbon is a vinyl-substituted aromatic hydrocarbon.

14. The composition oi claim 9 wherein the thiol is an alkyl thiol.

15. The composition of claim 9 wherein the thiol is an aryl thiol.

16. The composition of claim 9 wherein the thiol is a heterocyclicthiol.

17. A sulfur-containing viscous oil of lubricating viscosity obtainedby: condensing about 45 molar proportions of n-octene-l with about 5.5molar proportions of styrene and with one molar proportion of n-butylthiol at about 600 F. for about ten hours.

18. A sulfur-containing viscous oil of lubricating viscosity obtainedby: condensing about 45 molar proportions of n-decene-l with about 5.5molar proportions of styrene and with one molar proportion of t-butylthiol at about 650 F. for about ten hours.

19. A sulfur-containing viscous oil of lubri cating viscosity obtainedby: condensing about 375 molar proportions of n-decene-1 with about 50molar proportions of styrene and with one molar proportion of3-thiophenethiol at about 600 F. for about ten hours.

WILLIAM E. GARWOOD.

JOHN W. BROOKS.

ALEXANDER N. SACHANEN.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Certificate of Correction Patent No. 2,500,672

WILLIAM E. GARWOOD ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Column 3, line 19, for ankenyl read glkenyl; columns 7 and 8; Table I,tenth column thereof, opposite Run 17 for 0.936 read 0.9036 columns 11March 14, 1950 and 12, Table 11, second column thereof, opposite Run 12,for 12.3 read 7 and that the said Letters Patent should be read ascorrected aboue, so that the same may conform to the record of the casein the Patent Ofiice. Signed and sealed this 19th day of December, A. D.1950.

THOMAS F. MURPHY,

I Assistant Commissioner of Patents.

1. THE METHOD OF PREPARATION OF A VISCOUS OIL, WHICH COMPRISES:CONDENSING, AT A TEMPERATURE BETWEEN ABOUT 500*F. AND ABOUT 800*F. FOR APERIOD OF TIME SUFFICIENT TO EFFECT CONDENSATION, ONE MOLAR PROPORTIONOF A NORMAL, ALPHA MONOOLEFIN HAVING FROM FIVE TO EIGHTEEN CARBON ATOMSPER MOLECULE, FROM ABOUT 0.1 TO ABOUT ONE MOLAR PROPORTION OF ACONJUGATED OLEFINIC HYDROCARBON AND FROM ABOUT 0.001 TO ABOUT ONE MOLARPROPORTION OF A THIOL.
 17. A SULFUR-CONTAINING VISCOUS OIL OFLUBRICATING VISCOSITY OBTAINED BY: CONDENSING ABOUT 45 MOLAR PROPORTIONSOF N-OCTENE-1 WITH ABOUT 5.5 MOLAR PROPORTIONS OF STYRENE AND WITH ONEMOLAR PROPORTION OF N-BUTYL THIOL AT ABOUT 600*F. FOR ABOUT TEN HOURS.